Method for coating using molten organosiloxane compositions

Abstract: Organosiloxane compositions comprising specified combinations of MQ resins and liquid polyorganosiloxanes are applied as molten materials to form coatings that are non-flowable under ambient conditions and that can initially be remelted by heating the coating above its flow transition temperature. In the presence of moisture, the flow transition temperature of the coating gradually increases due to the reaction of hydrolyzable groups on the polyorganosiloxane ingredient until the coating is converted to a non-flowable, resin reinforced elastomer. Preferred coatings are non-transferable at 25°C. within ten minutes following application.

Description: This invention relates to a method for applying protective silicone coatings to substrates. This invention involves heating a specified class of moisture reactive organosiloxane compositions to a flowable state and applying the compositions as coatings to a substrate, whereupon the compositions cool and become non-flowable. The initially applied coatings are made flowable by heating but in the presence of atmospheric moisture the coatings gradually convert to a resin-reinforced elastomeric material that is not reflowable with subsequent heating to temperatures well above the application temperature. Many of these coatings can be handled within minutes after being coated without damage to the coating or transfer of the coating material. The cured coatings provide long term protection for substrates against harsh environments at temperatures above the application temperature of the initial coating. Many combinations of resinous and liquid polymers are well known. Some exhibit the properties characteristic of pressure sensitive adhesives, also referred to as PSA's. PSA's based on organosilicon compounds typically contain 1) a silicone resin with specified concentrations of monofunctional R 3 SiO units, referred to as M units, and tetrafunctional SiO 4/2 units, referred to as Q units, and 2) a high molecular weight polydiorganosiloxane having the consistency of a gum. These compositions are typically applied as a solution in a compatible organic liquid or a low viscosity, liquid non-reactive polyorganosiloxane. Following application of the solution to a desired substrate the liquid is evaporated to deposit the PSA. The prior art is represented by the following: EP-A2 0,529,841; US-A 4,143,088; US-A 4,515,932; US-A 4,753,977; US-A 4,990,364; US-A 5,070,121; US-A 5,091,484; JP-A 64/251,827 and JP-A 04/81,487. When curable compositions are applied in the molten state (as "hot melts") and are used as protective coatings, the cooled uncured compositions should preferably exhibit sufficient adhesion and low tackiness to allow the coated articles to be handled either immediately, or shortly following application, without damage to the coating or transfer of the coating material to objects in contact with the articles. When the substrate is a printed circuit board, it is desirable that the interior portion of the coating remain reflowable upon heating for a limited time to correct coating defects and to make repairs of electronic components mounted on the coated substrate. Ultimately, a crosslinked, non-reflowable elastomeric material is formed under ambient conditions to exhibit excellent adhesion to the substrate, as demonstrated by a resistance to corrosion of metal surfaces and articles mounted on the substrate. With increasing emphasis on eliminating or at least reducing the amount of volatile materials released during the application and curing of coating compositions, there has been a growing demand for curable compositions that can be applied in the absence of solvents or diluents. It is, therefore, an object of the present invention to provide moisture reactive coating compositions that are substantially free of unreactive liquid materials and are also heated for application as molten liquids. Upon contacting a substrate at ambient temperature, this coating composition rapidly forms solid coatings which exhibit strong adhesion to clean or contaminated substrates without requiring a primer or surface preparation. The initially applied coatings are reflowable upon heating and under ambient conditions are gradually converted by moisture curing to substantially tack-free, resin-reinforced elastomeric materials. These materials are not reflowable even at temperatures substantially above their application temperature and will maintain their initial adhesion to the substrate. We have unexpectedly found that this objective can be achieved by using organosiloxane compositions containing predetermined combinations of organosiloxane MQ resins and liquid polyorganosiloxanes of specified viscosity and functionality. Preferred compositions exhibit excellent adhesion to a variety of organic and metallic substrates. This invention provides a method for coating at least one surface of a substrate, the method comprising the sequential steps of I) causing a curable coating composition to become flowable by heating the composition above its flow-transition temperature, where the coating composition comprises (a) a resinous organosiloxane copolymer exhibiting a number average molecular weight of at least 1000 and comprising monovalent R 1 3 SiO 1/2 units, tetravalent SiO 4/2 units and up to six weight percent, based on the weight of said copolymer, of XSiO 3/2 units, where X is at least one member selected from hydroxyl groups, hydrolyzable groups and trihydrocarbylsiloxy groups, and (b) a polyorganosiloxane that is liquid at 25°C. and contains an average of more than two hydrolyzable groups per molecule, where R 1 represents a monovalent unsubstituted or substituted hydrocarbon radical, at least 80 percent of the repeating units of said polyorganosiloxane are disiloxane units and the amount of said resinous organosiloxane copolymer relative to said polyorganosiloxane is sufficient for 1) a coating comprising a 0.075 mm thick vertical layer of said composition to be substantially non-flowable at 25°C. and 2) said composition to have a flow transition temperature within the range from 40 to 200°C. prior to reaction of said hydrolyzable groups, II) applying said composition as a flowable material to a surface of a substrate to form a coating, and III) exposing the coating to moisture for a time sufficient to react said hydrolyzable groups and to increase the flow transition temperature of said composition by at least 10°C. At least a portion of the hydrolyzable groups present on the polyorganosiloxane ingredient, ingredient (b), are derived from silanol groups on an initial reactant. In this instance, the curable composition contains at least an equimolar quantity, based on the number of silanol groups, of a silane or other low molecular weight organosilicon compound having at least three hydrolyzable groups per molecule. It will be understood that a reaction will occur between the silane and the silanol groups present in the precursor to ingredient (b), particularly if a catalyst promoting this reaction is present in the composition. The ingredients present in the curable organosiloxane compositions used as coating materials in the present method include at least one resinous organosiloxane copolymer comprising triorganosiloxy and SiO 4/2 units, referred to as MQ resins, and at least one polyorganosiloxane with a viscosity of from 0.02 to 100 Pa·s at 25°C. The present method is based on the identification of certain MQ resins and liquid polyorganosiloxanes and a range of relative concentrations within which these ingredients form a flowable melt at temperatures from 40 to 200°C. and are non-flowable at about 25°C. The melt can be applied as a coherent, uniform layer on a variety of organic and inorganic substrates using conventional coating techniques. As the temperature of our compositions decreases from the heated temperature at which it flows to the ambient temperature of the substrate, typically about 25°C., there is a narrow temperature range where our composition undergoes a transition from a material that flows (a useful coating material) to one that does not flow. This transition typically occurs within a one minute period when applied on a vertical substrate. For the present compositions this layer is preferably about 0.003 inch (0.075 mm) thick. Lower viscosity compositions will gradually drip off the surface when applied in this thickness. Another way of defining the non-flowing characteristic of our curable compositions at 25°C. is to fill a 60 cm 3 capacity jar with a molten composition of this invention to one-third of its capacity. The composition is allowed to solidify and the jar is then placed on its side. There should be no evidence of flowing during a twenty minute period. This test result is equivalent to a minimum room temperature dynamic viscosity in the approximate range of from 2 x 10 7 to 8 x 10 7 centipoise (20 to 80 kPa·s) when measured at 1 radian. In the presence of moisture, the hydrolyzable groups on the polyorganosiloxane ingredient of our compositions will crosslink to gradually convert the composition to substantially tack-free, resin-reinforced elastomeric materials. These crosslinked materials will then no longer flow at the temperature used to apply the coating. During the initial stages of this conversion, the flow transition temperature of our composition does not appreciably increase and the composition can be reflowed by heating to temperatures of from 60 to 200°C. During conversion of our compositions from materials that flow at elevated temperatures to a non-flowable resin reinforced elastomer by the curing reaction of hydrolyzable groups, the flow transition temperature of the composition increases by at least 10°C., preferably by at least 50°C., relative to the initial composition. In most instances, the final composition may soften but will not flow at temperatures up to 200°C. The flow characteristics of our curable compositions change when heated above their flow transition temperature to the extent that they are readily extruded from conventional dispensers used to apply "hot melt" compositions. The dynamic viscosity of these compositions decreases to not more than 10 Pa·s at a temperature not exceeding 200°C. Preferred compositions become non-transferable within ten minutes after cooling to ambient temperature on the surface of the substrate. The term "non-transferable" used to define our preferred coating compositions implies that when an object at ambient temperature contacts the surface of a coating that has cooled to the temperature of the substrate, no material is transferred from the coating to the object. The flow transition temperature and other rheological properties of a composition of our invention can be varied by selection of a particular MQ resin, also referred to herein as "resin" and polyorganosiloxane, referred to as "polymer" and by variation of the relative concentrations of these two ingredients. It should be understood that inclusion of two or more different resins and polymers will affect not only the flow characteristics of the blend but also the properties of the product obtained following reaction of the hydrolyzable groups present on the polymer to form a crosslinked resin reinforced elastomer. The relative concentrations of resin and polymer required to achieve the optimum combination of properties of the present compositions is dependent in part on the molecular weights of these ingredients. A convenient way of expressing the relative concentration ranges for MQ resin and liquid polyorganosiloxane is in terms of the melt viscosity of the mixture prior to reaction of the hydrolyzable groups. This value is typically less than about 10 Pa·s at the temperature used to apply coatings of the present method. This is in addition to the requirements that a 0.003 inch (0.075 mm) thick layer of the composition is non-flowable on a vertical surface under ambient conditions and that the composition remains reflowable with heating during the early stages of the conversion to a resin-reinforced elastomer. For preferred combinations of MQ resins and liquid polyorganosiloxanes encompassed by the present invention the resin constitutes from 40 to 80 percent of the combined weight of the resin and the liquid polyorganosiloxane. Compositions containing less than about 40 weight percent of even the highest molecular weight resins are flowable at 25°C. This is true even when the resin is the highest molecular weight resin that will form a flowable composition in the present method. Compositions containing more than 80 weight percent of even the lowest molecular weight resins of this invention are difficult to process. Conventional melt coating techniques at temperatures up to 200°C. are unsuccessful or form coatings that are brittle. Curing agents and/or curing catalysts can further be a part of the present composition. The requirement for the presence of these materials to form a useful coating is dependent upon the types of reactive groups present on the resinous copolymer(s), on the liquid polyorganosiloxane(s) and the desired curing reaction. The resinous copolymer constitutes one of the two types of organosiloxane materials present in compositions used in our method. The resins contain monofunctional (M) units represented by the formula R 1 3 SiO 1/2 and tetra-functional (Q) units represented by the formula SiO 4/2 . R 1 represents a substituted or unsubstituted monovalent hydrocarbon radical. Resins of this type are well known in the art as one of the ingredients present in organosiloxane compositions used in PSA's. The MQ resins are soluble in liquid hydrocarbons such as benzene, toluene, xylene and heptane or in liquid organosilicon compounds such as a low viscosity cyclic and linear polydiorganosiloxanes. In the R 1 3 SiO 1/2 or M unit, R 1 preferably represents a monovalent hydrocarbon radical containing preferably up to 20 carbon atoms and most preferably from 1 to 10 carbon atoms. Examples of suitable hydrocarbon radicals for R 1 include alkyl radicals, such as methyl, ethyl, propyl, pentyl, octyl, undecyl and octadecyl; alkenyl radicals, such as vinyl, allyl and 5-hexenyl; cycloaliphatic radicals, such as cyclohexyl and cyclohexenylethyl; and aryl radicals such as phenyl, tolyl, xylyl, benzyl and 2-phenylethyl. Typical substituted hydrocarbon radicals represented by R 1 include chloromethyl and 3,3,3-trifluoropropyl. At least one-third, preferably at least two-thirds, of the R 1 radicals in the formula for the M unit of the MQ resin are methyl radicals. Examples of preferred M units HMe 2 SiO 1/2 , Me 3 SiO 1/2 , PhMe 2 SiO 1/2 and Me 2 ViSiO 1/2 where Me, Ph and Vi denote methyl, phenyl and vinyl, respectively. The resin may contain two or more of these units. The molar ratio of the M to Q units in the MQ resin is typically from 0.5/1 to 1.5/1, preferably from 0.6/1 to 0.9/1. These mole ratios are conveniently measured by 29 Si nuclear magnetic resonance (NMR) spectroscopy. This technique is capable of quantitatively determining the molar contents of: M(resin), M(neopentamer), Q (resin), Q(neopentamer) and hydroxyl groups. For the present invention, the M/Q ratio {M(resin) + M(neopentamer)}/(Q(resin) + Q(neopentamer)} represents the ratio of the total number of triorganosiloxy groups in the resinous and neopentamer portions of the copolymer to the total number of silicate groups in the resinous and neopentamer portions of the copolymer. It will be understood that the neopentamer portion includes only that amount inherently present in the copolymer as it is prepared. The concentration of silanol groups present in the resin can be determined by Fourier Transform Infrared Spectrophotometry (FTIR). Silicon-bonded terminal groups that are present in the MQ resin include reactive groups such as silanol, silicon-bonded hydrogen, alkenyl radicals and hydrolyzable groups, like alkoxy such as methoxy, alkenyloxy such as isopropenyloxy, ketoximo such as methylethylketoximo, carboxy such as acetoxy, amidoxy such as acetamidoxy and aminoxy such as N,N-dimethylaminoxy. Alternatively, the terminal groups present on the resin can be unreactive groups such as trihydrocarbylsiloxy. When reactive groups are present they typically constitute up to 6 weight percent of the MQ resin. It will be understood that silanol groups are present only in the absence of a suitable catalyst for the reaction of these silanol groups with the alkoxy or other hydrolyzable groups present on the polyorganosiloxane ingredient of our compositions. To maximize the storage stability of the present compositions under ambient conditions, the silanol groups formed during preparation of the MQ resin are converted to either a trihydrocarbylsiloxy group or a hydrolyzable group. Conversion is conveniently achieved by reacting the resin with a silane, disiloxane or disilazane containing the appropriate terminal group. Silanes containing hydrolyzable groups are typically added in excess of the quantity required to react with the silanol groups of the resin. These groups are responsible for conversion of our compositions from materials that are flowable with heating to resin reinforced elastomers that may soften but do not flow at temperatures from 60 to 200°C. If all of the initial silanol groups of the MQ resin are converted to triorganosiloxy groups by reaction with a monofunctional silane, disiloxane or disilazane, the copolymer will not participate in the reaction(s) used to cure the composition. The molecular weight required to achieve the desired flow characteristics of the MQ resin of our invention will depend in part on the molecular weight of the resin and the type(s) of hydrocarbon radicals, represented by R 1 , that are present in this ingredient. For the preferred resins where R 1 is alkyl containing from 1 to 3 carbon atoms, the number average molecular weight of the resin is preferably from 1500 to about 15,000, preferably from 2700 to 6500. The molecular weight of the MQ resin is conveniently determined by gel permeation chromatography with MQ resin standards rather than the conventional polystyrene standards. The MQ resin can be prepared by any suitable method. Such resins have been prepared by cohydrolysis of the corresponding silanes or by silica hydrosol capping methods. Our MQ resin is preferably prepared by the silica hydrosol capping processes of US-A(s) 2,676,182; 4,611,042 and 4,774,310. The intermediates used to prepare the MQ resin are typically triorganosilanes of the formula R 1 3 SiX, where X represents a hydrolyzable group and either a silane with four hydrolyzable groups such as halogen, alkoxy or hydroxyl or an alkali metal silicate such as sodium silicate. Non-reactive substituents that can be present on R 1 include halogen and cyano. To form useful coatings, the resinous organosiloxane copolymer should be a tack-free solid at 25°C. and soften sufficiently at a temperature from 40 to 200°C. The copolymer will then flow in the presence of the other ingredients of our coating composition under the operating conditions we use to apply our coatings to articles. The polyorganosiloxane ingredient of the coating compositions of our invention is a liquid at 25°C. and is composed of difunctional (D) repeating units of the formula R 2 R 3 SiO. The polymers can optionally contain up to 20 percent, based on total repeating units, of trifunctional (T) units of the formula R 4 SiO 3/2 . In these formulae, R 2 represents a hydrocarbyl radical selected from the same group as R 1 or an alkoxy group. R 3 and R 4 are individually selected from the same group as R 1 . At least 50 percent, preferably at least 80 percent, of the radicals represented by R 2 , R 3 and R 4 are lower alkyl, most preferably methyl. The total number of repeating units per molecule of the liquid polyorganosiloxane is equivalent to a viscosity of from 20 to 100,000 centipoise (0.02 to 100 Pa·s) at 25°C. A viscosity of from 0.05 to 25 Pa·s is preferred and can be achieved using a single polyorganosiloxane or a mixture containing two or more polyorganosiloxanes. The terminal units present on the liquid polyorganosiloxane are represented by the formula R 5 a Y 3-a SiG-, where Y is a hydrolyzable group, R 5 is selected from aminoalkyl in addition to the same group of substituted and unsubstituted hydrocarbon radicals as R 1 , G represents a divalent group linking the silicon atom of the terminal unit with another silicon atom and a is 0 or 1. If no curing agent, such as a silane containing at least three hydrolyzable groups per molecule, is present in the curable composition, the liquid polyorganosiloxane and/or the MQ resin should contain an average of more than two hydrolyzable groups per molecule in order to form a crosslinked product. Typical hydrolyzable groups, Y, include those described in the preceding section of this specification describing the resin ingredient. When a is 0, the groups represented by Y are preferably alkoxy or methylethyl ketoximo and R 5 is alkyl, such as methyl or ethyl or aminoalkyl such as aminopropyl or 3-(2-aminoethylamino)propyl. If an amino group is present on a hydrolyzable group, the amino group can be primary, secondary or tertiary. In the formula, G represents any divalent group or atom which is not hydrolyzable and links the silicon atom(s) of the terminal unit to another silicon atom of the liquid polyorganosiloxane ingredient such that the terminal unit is not removed during curing of the composition and the curing reaction is not adversely affected. Hydrolytically stable linkages represented by G include oxygen, hydrocarbylene such as alkylene and phenylene, hydrocarbylene containing one or more hetero atoms selected from oxygen, nitrogen and sulfur and combinations of these linking groups. G can also represent a silalkylene linkage such as -(OSiMe 2 )CH 2 CH 2 -, -(CH 2 CH 2 SiMe 2 ) (OSiMe 2 )CH 2 CH 2 -, -(CH 2 CH 2 SiMe 2 )O-, (CH 2 CH 2 SiMe 2 )OSiMe 2 )O-, -(CH 2 CH 2 SiMe 2 )CH 2 CH 2 - and -CH 2 CH 2 -, a siloxane linkage such as -(OSiMe 2 )O- or an oxygen atom. Specific examples of preferred terminal groups include (MeO) 3 SiCH 2 CH 2 -, (MeO) 3 SiO-, Me(MeO) 2 SiO-, H 2 NCH 2 CH 2 N(H)(CH 2 ) 3 SiO-, (EtO) 3 SiO-, (MeO) 3 SiCH 2 CH 2 Si-MeCH 2 CH 2 SiMe 2 O-, Me 2 NOSiO-, MeC(O)N(H)SiO- and CH2=C(CH3)OSiO-. Me in these formulae represents methyl and Et represents ethyl. In addition to the -CH 2 CH 2 - shown in some of the preceding terminal groups, the isomeric -CH(CH 3 )- radicals can also be present as a result of the hydrosilation reaction between a silicon-bonded vinyl radical and a silicon-bonded hydrogen atom. This reaction is used to form some of the present terminal units. A portion of the terminal units represented by R 5 a Y 3-a siG can be present on the MQ resin (depending upon whether the reactant used to form the terminal units is reacted with the MQ resin), the liquid polyorganosiloxane or a mixture of these ingredients. The terminal units of the polyorganosiloxane and MQ resin can be present on these initial reactants or they can be formed in situ. This would occur by reaction of the corresponding silanol, alkenyl or SiH-groups present on the precursor polyorganosiloxane and/or MQ resin with an organosilicon compound containing a desired terminal group in addition to a group that will react with the group present on the precursor polyorganosiloxane and/or resin. Organosilicon compounds that can be reacted with the silanol groups to form reactive terminal groups in the curable composition include silanes, disiloxanes, disilazanes and functionally substituted polydiorganosiloxanes. Silanes used to form hydrolyzable groups on the MQ resin or polyorganosiloxane can be represented by the general formula Y 3 SiG', where G' represents a group that will react with a silanol group, SiH or SiCH=CH 2 to form the desired linking group G. It will be understood that G' can be selected from the same group as Y. Disiloxanes can be represented by the formula (Y 3 Si) 2 O and disilazanes by the formula (Y 3 Si) 2 NH. In the following, Me represents the methyl radical for purposes of simplifying the formulae. It will be understood that other hydrocarbon radicals can be substituted for methyl. (MeO) 3 SiCH 2 CH 2 - radicals and (MeO) 3 SiCH 2 CH 2 SiMe 2 -OSiMe 2 CH 2 CH 2 - radicals are introduced into a vinyl-terminated polyorganosiloxane by use of organosilicon compounds having the formula (MeO) 3 SiH and (MeO) 3 SiCH 2 CH 2 SiMe 2 OSiMe 2 H, respectively. Moisture reactive groups having the formulae (MeO) 3 SiO- and Me(MeO) 2 SiO- are introduced into a silanol-terminated polyorganosiloxane by compounds having the formulae (MeO) 4 Si and Me(MeO) 3 Si, respectively. Alternatively, compounds having the formulae (MeO) 3 SiH and Me(MeO) 2 SiH, respectively, are used when the polyorganosiloxane contains silanol groups or alkenyl radicals such as vinyl and a platinum group metal or a compound thereof, as a hydrosilation reaction catalyst. It will be understood that other hydrolyzable groups such as alkenyloxy and carboxy can replace the alkoxy group. The liquid polyorganosiloxanes of the present compositions are preferably polydimethylsiloxanes containing three alkoxy or ketoximo groups or two alkoxy groups together with either an alkyl or aminoalkyl radical. Depending upon the reaction used to cure the present compositions and the reactive terminal units present on the MQ resin and the liquid polyorganosiloxane, storage stability and/or curing of the composition may be improved by the presence of a curing agent. Typically, this curing agent is a silane of the formula R 6 n SiZ (4-n) , where R 6 represents an alkyl or a phenyl radical and Z is a hydrolyzable group that reacts with the terminal groups of the liquid polyorganosiloxane under ambient conditions to form a cured material and n is 0 or 1. Suitable hydrolyzable groups represented by Z include alkoxy containing from 1 to 4 carbon atoms, carboxy such as acetoxy, ketoximo such as methylethylketoximo and aminoxy (NH 2 O-). When the silane is used to stabilize curable compositions containing resins with M n greater than 4000, the hydrolyzable group represented by Z is preferably ketoximo. Suitable curing agents include methyltrimethoxysilane, methyltris(methylethylketoximo)silane, methyltriethoxysilane, methyltriacetoxysilane, 3(2-aminoethylamino)propyltrimethoxysilane and alkyl orthosilicates such as ethyl orthosilicate. According to a particular embodiment of the invention, in the unit R 1 3 SiO½ R 1 is selected from alkyl, substituted alkyl, alkenyl, cycloalkyl and aryl radicals; the X groups on the copolymer are hydroxyl and the composition contains a stoichiometric excess relative to said hydroxyl groups of hydrolyzable groups on the polyorganosiloxane; the number average molecular weight of the copolymer is from 2700 to 6500, the terminal groups present on the polyorganosiloxane are selected from trimethoxysiloxy, methyldimethoxysiloxy and aminopropyldimethoxysiloxy; at least 50 % of R 2 and R 3 are methyl, and the composition includes a curing agent containing an average of more than two silicon-bonded hydrolyzable groups per molecule, preferably a silane of the formula R 6 n SiZ 4-n , where z represents a hydrolyzable group that reacts with the terminal groups present on said polyorganosiloxane, R 6 is a hydrocarbon radical selected from the same group as R 1 and n is 0 or 1. When the hydrolyzable group present on the polyorganosiloxane ingredient is alkoxy, we have found that the ability of the cured compositions to retain adhesion at elevated temperatures is improved when a phenyltrialkoxysilane such as phenyltrimethoxysilane is used as the silane. The presence of sufficient silane to react with at least a portion of the silanol groups on the MQ resin has been found particularly desirable using resins with number average molecular weights greater than 3000 to avoid gelling during preparation of the curable composition. When the silane is used for this purpose the hydrolyzable groups present on the silane are preferably oximo or carboxy such as acetoxy, this preference is based on the higher reactivity of these hydrolyzable groups, relative to alkoxy, with the silanol groups present on the MQ resin. Some of the reactions used to cure the present compositions either require a catalyst or proceed at a considerably more rapid rate in the presence of a catalyst. Suitable curing catalyst will depend upon the curing reaction and include tin salts of carboxylic acids, such as stannous octoate and dibutyltin dilaurate and organotitanium compounds such as tetrabutyl titanate and partially chelated derivatives of these salts with chelating agents such as acetoacetic acid esters and beta-diketones. The hydrolyzable groups can either be present on the liquid polyorganosiloxane or a portion can be present on one or more silanes or other organosilicon compounds that react during curing of the composition. To prevent premature curing of the composition, it should be stored in the absence of moisture prior to being heated and should be applied as described in this specification. The present compositions are prepared by blending the ingredients to homogeneity. Depending upon the molecular weights, the polymer and the MQ resin, the relative concentrations of these ingredients and the silanol content of the resin, it may be desirable to pre-react the silanol groups of a precursor polymer prior to adding the MQ resin. It has been found that compositions containing resins with an average of more than three silanol groups per molecule have a tendency to form gels in the presence of silanol-functional polymers, alkoxy functional silanes and catalysts such as organotitanium compounds. The melt viscosity of a curable composition containing the MQ resin and liquid polyorganosiloxane described in this specification is a convenient way of determining methods for applying coatings of the present method. Conventional coating methods suitable for use with molten materials include dipping, spraying, coextrusion and spreading of viscous materials using heated doctor blades, draw-down bars and calendar rolls. Molten materials of suitable viscosity can be extruded as preformed films onto the desired substrate, where they will eventually cure under ambient conditions. Alternatively, a preformed extruded film can be solidified on a non-adhering substrate in the absence of moisture, stored in a moisture impermeable container and subsequently applied to the substrate intended to be coated. While in contact with the substrate, the film is heated to bond it to the substrate and then exposed to moisture to convert it to a resin reinforced elastomer. Compositions with melt viscosities up to 10 Pa·s are suitable for spraying. Spraying of molten materials typically involves forcing the material under pressure from a heated storage container through a nozzle containing one or more orifices measuring from 0.1 to 2 mm. in diameter. To assist in dispersing the stream of liquid material emerging from the nozzle, the stream can be contacted with a rapidly moving current of a gas such as air or nitrogen or directed against a suitable baffle. Depending upon the distance between the storage container and the nozzle, it may be necessary to heat the conduit connecting the nozzle or other dispensing orifice and the storage container to avoid solidification of the composition in the conduit or to blend a heated gas with the composition prior to or during passage through the conduit. The pressure required to transport the molten material from the storage container to the dispensing orifice can be generated by admitting a pressurized gas such as dry nitrogen into the container or by equipping the container with a mechanical device such as a ram, piston or follower plate. Equipment to transport and dispense moisture sensitive materials are commercially available and can be adapted for use with the present compositions by equipping them with appropriate heating means. Compositions with melt viscosities too high for spraying can be applied to substrates by dipping the substrate into a melt of the coating composition or by dispensing molten material onto a heated substrate and allowing it to spread under its own weight or with the use of heated draw down bars or doctor blades. To avoid premature curing, the reservoir of molten material should be maintained under a moisture-free gas such as dry nitrogen. The rate at which the substrate is withdrawn from the reservoir is determined by the viscosity of the coating composition and the desired thickness of the coating. One advantage of the present compositions is that during the initial stage of the moisture activated conversion to a resin reinforced elastomer, imperfections and discontinuities in the initial coating can be repaired by heating the coating and/or the substrate to a temperature at which the coating composition will flow. The coating can then be reformed by mechanical means using a coating bar, doctor blade, coating knife or other suitable device. A convenient method for reflowing the coating is by directing a current of heated air against the surface of the coating. When used as a conformal coating for printed circuit boards, the ability of the present compositions to be flowable following application makes it possible to repair the coated surface of the substrate and repair or replace objects such as solid state devices and other electronic devices mounted on the surface of the substrate. Coatings prepared by the present method cure slowly in the amount of moisture typically contained in the atmosphere to form elastomeric materials. The time required for completion of the curing reaction ranges from several minutes to several days, depending upon the type of moisture-activated reaction, the presence of catalysts for reaction and the temperature of the substrate. The reactions occurring during conversion of the present moisture reactive compositions and the means for adjusting the rate of these reactions are sufficiently well understood that a detailed discussion in the specification is not required. The method and compositions of this invention can be used to apply protective coatings to a variety of organic and inorganic substrates. Organic substrates include natural and synthetic polymers. Examples of suitable polymers are polyesters, polyamides, polyolefins, polycarbonates, epoxide polymers, resins derived from formaldehyde and phenols or other co-reactants, melamine resins fluorine-containing polymers such as polytetrafluoroethylene and polymers such as polysulfones and other "engineering plastics". These polymers can be reinforced with glass or ceramic fibers and other known reinforcing agents. Inorganic substrates that can be coated using the present compositions include metals, particularly conductive metals such as copper and aluminum, glass and ceramics. The adhesion, solvent resistance and electrical properties of coatings prepared in our method make the coatings particularly useful as conformal coatings for printed circuit boards and other substrates which contain electrical or electronic components, particularly if they are exposed to heat, moisture or other adverse conditions during use. A particularly desirable property of the present coatings is their surface resistivity values, which are typically at least 10 15 ohms/cm 2 . The following examples describe typical curable compositions for the present method and preferred embodiments of this invention. The examples should not be interpreted as limitations on the scope of the accompanying claims. Unless otherwise indicated all parts and percentages in the examples are by weight and viscosities are the values measured at 25°C. The amounts of polydiorganosiloxane and solubilized resin required for a particular composition together with the silane and curing catalyst, when required, were combined under ambient conditions in a glass reactor and heated at a temperature of from 50 to 60°C. for 30 minutes, at which time the temperature applied to the reactants was increased and the contents of the flask were placed under reduced pressure until the temperature of the material in the reactor reached 90°C. or 130°C. under a pressure of no more than 1.3 kPa (10 mm. Hg.). In some instances, the maximum temperature was maintained for from 10 to 15 minutes to obtain a homogeneous molten material. Some of the compositions were applied as coatings to copper coated substrates using a heated draw-down bar with a gap of 0.01 inch (0.25 mm). Imperfections and discontinuities in the coating, resulting from agglomeration of the coating composition or other problems encountered during application of the composition, were repaired by heating the coating sufficiently to cause it to flow. Heating was achieved by directing a stream of air at a temperature of from 125 to about 200°C. toward the coated surface of the substrate. Example 1 This example describes coating compositions preferred for use in the present method and demonstrates their adhesion to copper metal and to copper metal coated with solder fluxes that can be applied without prior cleaning of the metal. Sets of five copper plated FR-4 boards, a glass fiber reinforced epoxide composite material used as printed circuit board by the electronics industry, were coated on one surface with a layer of one of the following "no clean" solder fluxes: Type SM351F manufactured by Alpha Metal Type 3590T manufactured by Hi-Grade Type 950E manufactured by Kester Type RMA 390 DH3 manufactured by Alpha Metal, and Type 201C manufactured by Senju. A copper plated board that had not been coated with a solder flux was also evaluated (control). After the substrates were coated on one surface with a solder paste, they were coated on the same surface with one of the coating compositions described in Table 1 using a heated draw-down bar. When allowed to cool to ambient temperature, all of the compositions solidified to non-flowable materials almost immediately upon contact with the substrate. They were also non-transferable within 10-30 minutes after being applied. For periods ranging from 0.1 to 24 hours, the compositions could be converted to flowable materials by heating them. At the end of this period the compositions had cured sufficently to form materials that could no longer be converted to flowable liquids by heating. Imperfections in the coating could be repaired by heating the substrate sufficiently to reflow the coating. All of the coatings were between 0.125 and 0.275 mm. thick. The coated substrates were allowed to cure for 5 to 7 days prior to being evaluated for their ability to prevent corrosion of the substrate by the vapor in a chamber containing salt water at a temperature of 90°C. and a containing salt water at a temperature of 90°C. and a relative humidity of 90%. The ability to prevent corrosion in areas adjacent to the discontinuities produced by a pattern of incisions into the coating was seperately used as an indication of the degree of adhesion of the coating to the substrate. Prior to being exposed in the salt water chamber, a plurality of cuts were made in the coatings on the surface that had been treated with the solder fluxes and on one surface of the control. The cuts formed a cross hatch pattern with lines about 1.5 mm. apart. Following a 100 hour exposure in the salt water chamber, the crosshatched areas of the samples were rated on a scale of from 0 (more than 65% of cross-hatched area covered by corrosion) to 5 (no evidence of corrosion). For each combination of MQ resin and liquid polyorganosiloxane, the ratings for the samples coated with the five solder fluxes and the sample without any solder flux were averaged and the resultant values appear in Table 1. The composition of the organosiloxane coatings applied to the substrates appear in the table as the percentages of MQ resin solids (resin) and liquid polydiorganosiloxane (polymer), based on the combined weight of these ingredients. These percentages exclude any solvents added together with the resin ingredient. The MQ resins are represented by numbers and the liquid polyorganosiloxanes (polymers) by letters, in accordance with the following definitions. Resin 1 - An 81 weight percent solution in xylene of an organosiloxane copolymer exhibiting a number average molecular weight of 2700 and containing trimethylsiloxy and SiO 4/2 units in a molar ratio of 1.1:1 and 3.2 weight percent of silicon-bonded hydroxyl groups based on the weight of the resin; Resin 2 - A 72 weight percent solution in xylene of an organosiloxane copolymer exhibiting a molecular weight of 5000, measured using gel permeation chromatography with a resin standard and comprising trimethylsiloxy and SiO 2 unit in a molar ratio of 0.6:1 and containing 2.6 weight percent of silicon-bonded hydroxyl groups, based on the weight of the solution; Resin 3 - A 62 weight percent solution in xylene of resin 2 wherein all but 0.8 percent of the silicon-bonded hydroxyl groups were replaced by trimethylsiloxy groups. The number average molecular weights of the resins were determined by gel-permeation chromatography (GPC) using Varian TSK 4000 + 2500 columns at 35°C., a chloroform mobile phase at 1 mL/min and an IR detector set at 9.1 micrometers to detect Si-O-Si. The GPC was calibrated using narrow fractions of similar resins as standards. The Mn values reported herein exclude any neopentamer, (Me3SiO)4Si, present in the resin component. The trimethylsiloxy/SiO4/2 ratio of the resins was determined by 29Si NMR and the reported results include any neopentamer component present in the resin. Polydiorganosiloxane A - A 50 weight percent solution in isopropanol of a polydimethylsiloxane prepared by reacting a silanol terminated polydimethylsiloxane exhibiting a viscosity of 0.075 Pa·s with a stoichiometric excess, based on silicon-bonded hydroxyl groups, of 3(2-aminoethylamino)propyltrimethoxysilane; Polydiorganosiloxane B - A methoxy terminated dimethylsiloxane/phenylmethoxysiloxane/phenylsilsesquioxane copolymer prepared by reacting 41 parts of phenyltrimethoxysilane silane with 56 parts of cyclic dimethylsiloxanes in the presence of a Lewis acid catalyst. Polydiorganosiloxane C - A reaction product of 75 parts of a silanol terminated polydimethylsiloxane exhibiting a viscosity of about 0.04 Pa·s at 25°C. and containing 4 weight percent silanol groups, 15 parts of 3(2-aminoethylamino)-propyltrimethoxysilane and 10 parts of methyltrimethoxysilane. Polydiorganosiloxane D - A reaction product of a silanol-terminated polydimethylsiloxane having an average degree of polymerization of 40 with a stoichiometric excess of methyl tris(methylethylketoximo)silane. Polydiorganosiloxane E - A reaction product of a silanol-terminated polydimethylsiloxane having an average degree of polymerization of 40 with a stoichiometric excess of methyl-trimethoxysilane. Some of the compositions contained 0.5 weight percent, based on the weight of the composition, of tetrabutyl titanate (TBT) as a curing catalyst. The reactions used to cure the compositions are represented by Roman numerals as follows: I SiOH (on resin) + Si-OCH 3 (on polymer) → Si-O-Si + methanol (by product) IV SiOH (on polymer) (via hydrolysis of methoxy group) + Si-OCH 3 (on polymer) → Si-O-Si + methanol (by product) All of the compositions evaluated were non-transferable within ten minutes after being applied and could be remelted until fully cured, which usually required from 0.1 to 24 hours. Cure Composition Catalyst Salt Water Reaction Resin (%) Polymer (%) Corrosion I 1 (72) A (28) None 5 I 1 (70) A (30) TBT 5 I 2 (44) A (56) TBT 5 II 3 (62) D (38) TBT 2 III 2 (72) B (28) TBT 0 IV 3 (40) C (60) TBT 2 V 3 (62) E (38) TBT 3 Example 2 This example demonstrates the effect of the molecular weight of the liquid polyorganosiloxane on the ability of a composition of this invention to be applied as a uniform coating by spraying. Curable compositions were prepared as described in Example 1 using Resin 2 with three different methyldimethoxy-terminated polydimethylsiloxanes exhibiting average degrees of polymerization (Dp) of 40, 400 and 880. The weight ratio of resin to polydimethylsiloxane was 60:40. The compositions were applied to copper plated FR-4 boards by spraying using the following procedure: The curable composition was poured while molten from the reactor in which it was prepared into a cylindrical aluminum cartridge of the type used to dispense sealants. One end of the cylinder was fixed in position and contained a sealed opening through which material could be ejected from the cartridge. The other end of the cartridge was a filled with the molten curable compositions material, at which time a movable metal disk was inserted. Pressure was subsequently applied to the disk to force the contents of the cartridge through an opening made by puncturing the seal in the other end of the cartridge. The opening was sealed during cooling of the compositions, all of which were non-flowable under ambient conditions. When the composition had solidified in the cartridge, the seal of the cartridge was punctured and the cartridge placed in a sealable container equipped with an electrically operated heating element. The container was equipped with a pressure regulator that during operation exerted pressure against the movable disk of the cartridge. The cartridge container was then sealed and subsequently pressurized using compressed air. The container was equipped with a 1.2 mm-diameter spray nozzle through which the molten composition from the cartridge was forced as a continuous stream or droplets under a pressure of 138.0 to 517.4 kPa (20 to 75 psi) gage pressure and deposited onto a substrate located from 2 to 15 cm. from the nozzle. A compressed air outlet located at the nozzle cause the stream emerging from the nozzle to travel in a circular spiral toward the substrate. The temperature within the cartridge container was gradually raised from 90 to 150°C. in ten degree increments. At each increment compressed air was admitted into the container and the resultant pressure exerted by the movable disk, forced composition from the cartridge through the nozzle and on to the surface of the substrate. The appearance of the resultant uncured coatings were evaluated and the results are summarized in Table 2. Example 3 This example demonstrates that coatings cannot be prepared using resin to polyorganosiloxane ratios below the lower limit of the present method. Curable compositions were prepared and applied to a copper-coated FR-4 board using the procedure described in Example 1 with Resin 3 and a methyldimethoxy terminated polyorganosiloxane exhibiting a Dp of 880 at resin to polyorganosiloxane weight ratios of 5:95 (A), 30:70 (B) and 40:60 (C). Tetrabutyl titanate was used as the curing catalyst at a concentration of 0.5 weight percent for A and 0.4 percent for B and C. The coatings were evaluated for transferability by touching them. Uncured material was still transferable from coatings prepared from A and B one hour after the coatings had been applied. The coating prepared from C did not convert to a non-transferable material until it cured, which required about one hour and was thereafter not remeltable. None of the three compositions evaluated were both non-transferable and remeltable in the uncured form.

Claims: A method for coating at least one surface of a substrate, the method comprising the sequential steps of I) causing a coating composition to become flowable by heating the composition above its flow-transition temperature, where the coating composition comprises (a) a resinous organosiloxane copolymer exhibiting a number average molecular weight of at least 1000 and comprising monovalent R 1 3 SiO 1/2 units, tetravalent SiO 4/2 units and up to 6 weight percent, based on the weight of said copolymer, of XSiO 3/2 units, where X is at least one member selected from hydroxyl groups, silicon-bonded hydrogen, hydrolyzable groups and trihydrocarbylsiloxy units, and (b) a polyorganosiloxane that has a viscosity of from 0.02 to 100 Pa.s at 25°C. and contains an average of more than two hydrolyzable groups per molecule, where R 1 represents a monovalent unsubstituted or substituted hydrocarbon radical, provided that at least one third are methyl radicals, at least 80 percent of the repeating units of said polyorganosiloxane are diorganosiloxane units in an amount cf 40 to 80 weight percent of said resinous organosiloxane copolymer (a) relative to the combined weight of (a) and (b) to provide 1) a coating comprising a 0.075 mm. thick vertical layer of said composition to have a minimum room temperature dynamic viscosity in the range of from 20 to 80 kPa.s (2 x 10 7 to 8 x 10 7 centipoise) and 2) said composition to have a flow transition temperature within the range from 40 to 200°C. prior to reaction of said hydrolyzable groups, II) applying said composition as a flowable material, having a melt viscosity prior to reaction of the hydrolysable groups of less than 10 Pa.s, to a surface of a substrate to form a coating, and III) exposing the coating to moisture for a time sufficient to react said hydrolyzable groups and to increase the flow transition temperature of said composition by at least 10°C. A method according to claim 1 wherein the polyorganosiloxane (b) contains up to 20 percent, based on total repeating units, of trifunctional units of formula R 4 SiO 3/2 where R 4 is independently selected from the same groups as R 1 . A method according to claim 1 or 2, where R 1 contains up to 20 carbon atoms, the molar ratio of monovalent to tetravalent units in said copolymer is from 0.5:1 to 1.5:1, up to 20 percent of the repeating units in said polyorganosiloxane are trifunctional units, with the remainder being diorganosiloxane units of the formula R 2 R 3 SiO, where R 2 is an alkoxy group or a monovalent unsubstituted or substituted hydrocarbon radical, R 3 is a monovalent unsubstituted or substituted hydrocarbon radical, with the proviso that at least 50 percent of the radicals represented by R 2 and R 3 are ethyl and/or methyl, the terminal units present on said polyorganosiloxane are represented by the formula R 5 a Y 3-a SiG, where R 5 is selected from aminoalkyl radicals and monovalent unsubstituted and substituted hydrocarbon radicals, Y is a hydrolyzable group, G represents a divalent group linking the silicon atom of the terminal unit with another silicon atom and a is 0 or 1, the viscosity of said polyorganosiloxane is from 0.02 to 100 Pa·s at 25°C., said resinous organosiloxane copolymer constitutes from 40 to 80 percent of the combined weight of said copolymer and said polyorganosiloxane and said layer is 0.075 mm thick. A method according to claim 3, where R 1 contains from 1 to 10 carbon atoms, the molar ratio of monovalent to tetravalent units in said copolymer is from 0.6 to 0.9; the number average molecular weight of said copolymer is from 1500 to 15,000; at least 80 percent of the hydrocarbon radicals represented by R 2 , R 3 are ethyl and/or methyl; R 5 is methyl, ethyl or aminoalkyl; the viscosity of said polyorganosiloxane at 25°C. is from 0.05 to 25 Pa·s; Y is selected from alkoxy, ketoximo, alkenyloxy, carboxy, amidoxy and aminoxy when a is 0 and Y is alkoxy when a is 1; G is oxygen; and an uncured coating formed using said composition is non-transferable under ambient conditions within 10 minutes after being applied. A method according to claim 4, wherein R 1 is selected from alkyl, substituted alkyl, alkenyl, cycloalkyl and aryl radicals; the X groups on said copolymer are hydroxyl and said composition contains a stoichiometric excess relative to said hydroxyl groups of hydrolyzable groups on the polyorganosiloxane; the number average molecular weight of said copolymer is from 2700 to 6500, the terminal groups present on said polyorganosiloxane are selected from trimethoxysiloxy, methyldimethoxysiloxy and aminopropyldimethoxysiloxy; at least 50 % of R 2 and R 3 are methyl, said composition includes a curing agent containing an average of more than two silicon-bonded hydrolyzable groups per molecule. A method according to claim 5, where said curing agent is a silane of the formula R 6 n SiZ 4-n , where Z represents a hydrolyzable group that reacts with the terminal groups present on said polyorganosiloxane, R 6 is a hydrocarbon radical selected from the same group as R 1 and n is 0 or 1. A method according to any of claims 1 to 6, where said composition contains a catalyst to facilitate curing of said composition, R 6 is alkyl, Z is alkoxy, alkenyloxy, carboxy, ketoximo or aminoxy. A method according to claim 7, wherein Z is alkoxy containing from 1 to 4 carbon atoms and said layer is applied by spraying or by spreading said composition over a surface of said substrate using an applicator heated to a temperature above the softening temperature of said composition. A method according to claim 1, where said composition is prepared by (1) preparing said polyorganosiloxane by reacting a polyorganosiloxane having silanol groups in the terminal positions with a silane of the formula R 6 n SiZ 4-n where R 6 represents an alkyl or phenyl radical, n is 0 or 1 and Z is a hydrolyzable group that reacts with said silanol groups in the presence of a suitable catalyst and (2) adding said resinous organosiloxane copolymer to the resultant reaction mixture containing said polyorganosiloxane. A method according to claim 1, wherein the flow transition temperature of said composition is increased by at least 50°C. following reaction of said hydrolyzable groups. A method according to claim 10, where the flow transition temperature of said composition following reaction of said hydrolyzable groups is at least 200°C.

Inventors: CIFUENTES MARTIN ERIC, STRONG MICHAEL RAYMOND, VANWERT BERNARD, CIFUENTES, MARTIN ERIC, STRONG, MICHAEL RAYMOND, VANWERT, BERNARD
Applicants: DOW CORNING, DOW CORNING CORPORATION
Application year: 1994
Main classification: C09D183
IPC codes: C09D183, B05D3, H05K3, B05D7